The activation of elemental phosphorus has been widely investigated for decades in attempts to develop more sustainable pathways to phosphorus-containing chemicals and materials. Phosphorus-rich anionic species have a special place in this chemistry due to the diversity of their structures and reactivities. Most pathways to polyphosphides rely on solid-state reactions between metals and red phosphorus, which demand elevated temperatures and several day long reaction times. Unique polyphosphide species have been generated in solution where white phosphorus is a main reactant due to its high reactivity and solubility. This allotrope, however, is pyrophoric and toxic, which makes its usage very restricted.<br/>We have been interested in the solution synthesis of polyphosphides, in particular, because this route affords highly soluble and reactive species, which can be further modified, in contrast to the solid-state reaction products, which are typically much more inert. To circumvent the need for the highly hazardous white phosphorus, we have developed the new synthetic method to activate red phosphorus with organic nucleophiles. Our earlier results have demonstrated that the nucleophilic attack on the elemental red phosphorus successfully leads to a variety of soluble polyphosphide anions as shown by NMR and X-ray measurement. In this contribution, we report a comprehensive study of this activation process in a wide range of solvents and organic nucleophiles. The possibilities of controlled synthesis of specific polyphosphides based on the polarity of reaction medium, activation temperature, and nucleophilic strength of activator will be presented.

Nucleophilic activation of red phosphorus into soluble polyphosphide anions

2019 Spring National Meeting

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